NO168249B - PREPARATION OF LATEXES OF VINYL CHLORIDE POLYMERS. - Google Patents
PREPARATION OF LATEXES OF VINYL CHLORIDE POLYMERS. Download PDFInfo
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- NO168249B NO168249B NO870966A NO870966A NO168249B NO 168249 B NO168249 B NO 168249B NO 870966 A NO870966 A NO 870966A NO 870966 A NO870966 A NO 870966A NO 168249 B NO168249 B NO 168249B
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- Prior art keywords
- polymerization
- monomer
- tert
- butyl
- para
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 13
- 229920000642 polymer Polymers 0.000 title description 7
- 239000000178 monomer Substances 0.000 claims description 49
- 238000006116 polymerization reaction Methods 0.000 claims description 34
- 239000006185 dispersion Substances 0.000 claims description 21
- 239000003999 initiator Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 15
- 239000012429 reaction media Substances 0.000 claims description 15
- 239000012736 aqueous medium Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000003505 polymerization initiator Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012874 anionic emulsifier Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000012875 nonionic emulsifier Substances 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- 239000004816 latex Substances 0.000 description 9
- 229920000126 latex Polymers 0.000 description 9
- -1 vinylidene halides Chemical class 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000003995 emulsifying agent Substances 0.000 description 7
- 101000823778 Homo sapiens Y-box-binding protein 2 Proteins 0.000 description 6
- 206010039509 Scab Diseases 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- YFZCNXJOYHYIGC-UHFFFAOYSA-N (2,2,2-trichloroacetyl) 2,2,2-trichloroethaneperoxoate Chemical compound ClC(Cl)(Cl)C(=O)OOC(=O)C(Cl)(Cl)Cl YFZCNXJOYHYIGC-UHFFFAOYSA-N 0.000 description 1
- LACJUMMFBDWVHD-UHFFFAOYSA-N (2,2-dichloroacetyl) 2,2-dichloroethaneperoxoate Chemical compound ClC(Cl)C(=O)OOC(=O)C(Cl)Cl LACJUMMFBDWVHD-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- YXZXVSUJOWPVHP-UHFFFAOYSA-N carboxyoxy 2-methylpropyl carbonate Chemical compound CC(C)COC(=O)OOC(O)=O YXZXVSUJOWPVHP-UHFFFAOYSA-N 0.000 description 1
- KHBQOOHGCZONAK-UHFFFAOYSA-N carboxyoxy ethyl carbonate Chemical compound CCOC(=O)OOC(O)=O KHBQOOHGCZONAK-UHFFFAOYSA-N 0.000 description 1
- VZBZCLRLPBEOBO-UHFFFAOYSA-N carboxyoxy octan-3-yl carbonate Chemical compound CCCCCC(CC)OC(=O)OOC(O)=O VZBZCLRLPBEOBO-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- BSVQJWUUZCXSOL-UHFFFAOYSA-N cyclohexylsulfonyl ethaneperoxoate Chemical compound CC(=O)OOS(=O)(=O)C1CCCCC1 BSVQJWUUZCXSOL-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 1
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Gjenstand for foreliggende oppfinnelse er fremstilling av latekser av homo- og kopolymerer av vlnylklorid der partiklen har en midlere diameter mellom 0,2 og 0,8 pm og inneholder minst en organooppløselig polymeriseringsinitiator, ved polymerisering i mikrosuspensjon av de tilsvarende monomerer. The object of the present invention is the production of latexes of homo- and copolymers of woolnyl chloride where the particle has an average diameter between 0.2 and 0.8 pm and contains at least one organo-soluble polymerization initiator, by polymerization in microsuspension of the corresponding monomers.
Partiklene av lateksene inneholder all den initiator som er nødvendig for polymerisering i podet mikrosuspensjon og polymeriseringen krever ikke komplementær tilsetning av polymeriseringsinitiator. The particles of the latexes contain all the initiator necessary for polymerization in the grafted microsuspension and the polymerization does not require the complementary addition of polymerization initiator.
Som brukt heri betyr uttrykket polymerisering "i mikrosuspensjon" eller "finsuspensjon" en polymerisering i nærvær av en organooppløselig initiator eller initiatorer av minst en monomer dispergert ved omrøring i et vandig medium inneholdende et emulgeringsmiddel som stabilisator. As used herein, the term polymerization "in microsuspension" or "fine suspension" means a polymerization in the presence of an organosoluble initiator or initiators of at least one monomer dispersed by stirring in an aqueous medium containing an emulsifier as a stabilizer.
FR-PS 1 485 547 viser at det ved fremstilling av vlnylklorid polymerer ved polymerisering i podet mikrosuspensjon er kjent som podingsprodukt å benytte en lateks hvis partikler inneholder all initiator som er nødvendig for polymeriseringen . FR-PS 1 485 547 shows that in the production of vinyl chloride polymers by polymerization in a grafted microsuspension, it is known as a grafting product to use a latex whose particles contain all the initiator necessary for the polymerization.
Prosedyrene som er benyttet til nu for fremstilling av en slik lateks ved polymerisering i mikrosuspensjon oppviser følgende mangler: i) under fremstilling av dispersjonen av monomeren eller monomerene og som utføres ved en temperatur som vanligvis ligger mellom 10 og 30°C, observeres så og si bestandig dannelse av skorpe som forstyrrer virkningen av de mekaniske innretninger som benyttes, og som derved fører til en lateks hvis midlere partikkeldla-meter ikke er reproduserbar fra en sats til en annen, The procedures used until now for the production of such a latex by polymerization in microsuspension exhibit the following shortcomings: i) during the production of the dispersion of the monomer or monomers and which is carried out at a temperature which is usually between 10 and 30°C, observed constant formation of a crust which interferes with the effect of the mechanical devices used, and which thereby leads to a latex whose mean particle diameter is not reproducible from one batch to another,
og/eller and or
ii) under polymeriseringen av monomeren eller monomerene som således er dispergert fører den store mengde tilstede-værende initiator som kan være lik mere enn 20 ganger ii) during the polymerization of the monomer or monomers which are thus dispersed, the large amount of initiator present, which can be equal to more than 20 times
mengden som er nødvendig for polymerisering, hyppig til en brå temperaturstigning i reaksjonsmediet og som kan overskride 10°C, og til dannelse av et stort antall skorper. the amount necessary for polymerization, often to a sudden temperature rise in the reaction medium and which can exceed 10°C, and to the formation of a large number of crusts.
Prosedyren som er gjenstand for oppfinnelsen tar sikte på å bøte på de nevnte mangler. The procedure which is the subject of the invention aims to remedy the aforementioned shortcomings.
Kort sagt omfatter oppfinnelsen en forbedring i en fremgangsmåte for fremstilling av latekser av homo- og kopolymerer av vlnylklorid, hvilke partikler har en midlere diameter mellom 0,2 og 0,8 pm og som inneholder minst en organooppløselig polymeriseringsinitiator, ved polymerisering i mikrosuspensjon av den eller de tilsvarende monomerer, i henhold til hvilken en fin dispersjon av monomeren eller monomerene dannes i et vandig medium inneholdende minst et anionisk emulgeringsmlddel eller minst et anionisk emulgeringsmlddel og minst et ikke-ionisk emulgeringsmlddel, i nærvær av 0,004 til 0,16 vekt-#, beregnet på vekten av monomer eller monomerer, av nevnte initiator, uttrykt som aktivt oksygen, og der det således dannede reaksjonsmedium underkastes polymerisering ved den ønskede polymeriseringstemperatur Øj_, og denne karakteriseres ved at den omfatter, til det vandige medium å tilsette 2 ,6-ditert.-butyl-para-cresol før man danner dispersjonen av monomer eller monomerer, og, i løpet av polymeriseringen, kontinuerlig å tilsette 2,6-ditert.-butyl-para-cresol til reaksjonsmediet når temperaturen i reaksjonsmediet Øg er slik at temperaturforskjellen Ø2-Ø1 ligger over en verdi valgt innen intervallet 0 - +5°C, og fortrinnsvis fra 0 - + 2' C. In short, the invention comprises an improvement in a method for the production of latexes of homo- and copolymers of vinyl chloride, which particles have an average diameter between 0.2 and 0.8 pm and which contain at least one organo-soluble polymerization initiator, by polymerization in microsuspension of the or the corresponding monomers, according to which a fine dispersion of the monomer or monomers is formed in an aqueous medium containing at least one anionic emulsifying agent or at least one anionic emulsifying agent and at least one nonionic emulsifying agent, in the presence of 0.004 to 0.16 wt-# , calculated on the weight of monomer or monomers, of said initiator, expressed as active oxygen, and where the reaction medium thus formed is subjected to polymerization at the desired polymerization temperature Øj_, and this is characterized by the fact that it includes, to the aqueous medium, adding 2,6- di-tert.-butyl-para-cresol before forming the dispersion of monomer or monomers, and, during the polymerization, continuously adding 2,6-di-tert.-butyl-para-cresol to the reaction medium when the temperature in the reaction medium Øg is such that the temperature difference Ø2-Ø1 lies above a value selected within the interval 0 - +5°C, and preferably from 0 - + 2'C.
Ifølge oppfinnelsen og før dannelsen av dispersjonen av monomer eller monomerer tilsettes 2,6-ditert.-butyl-para-cresol til det vandige medium og i løpet av polymeriseringen blir 2,6-ditert-.-butyl-para-cresol likeledes tilsatt på kontinuerlig måte til reaksjonsmediet når temperaturen til dette, 0£, er slik at temperaturforskjellen Ø2-Ø1 ligger over en verdi valgt innen intervallet 0 - +5'C og fortrinnsvis fra 0 til +2°C. Det er nu funnet at tilsetning av 2,6-ditert.-butyl-para-cresol til det vandige medium før man gjennomfører dispersjonen av monomeren eller monomerene, undertrykker dannelsen av skorpe og at tilsetningen i løpet av polymeri-seringsdriften under oppfinnelsens betingelser, begrenset til mindre enn 6°C temperaturforhøyelse i vesentlig grad reduserer dannelsen av skorper på dette trinn. Det er også observert at bruk av, under de samme betingelser, hydrokinon eller metylhydrokinon i stedet for 2,6-ditert.-butyl-para-cresol , kun i meget liten grad reduserer de nevnte mangler. According to the invention and before the formation of the dispersion of monomer or monomers, 2,6-di-tert-butyl-para-cresol is added to the aqueous medium and during the polymerization 2,6-di-tert-butyl-para-cresol is likewise added to continuous way to the reaction medium when the temperature of this, 0£, is such that the temperature difference Ø2-Ø1 lies above a value selected within the interval 0 - +5'C and preferably from 0 to +2°C. It has now been found that the addition of 2,6-di-tert.-butyl-para-cresol to the aqueous medium before carrying out the dispersion of the monomer or monomers suppresses the formation of crust and that the addition during the polymerization operation under the conditions of the invention, limited to less than 6°C temperature increase significantly reduces the formation of crusts at this stage. It has also been observed that the use, under the same conditions, of hydroquinone or methylhydroquinone instead of 2,6-di-tert.-butyl-para-cresol, only to a very small extent reduces the mentioned defects.
Tilsetningen av 2,6-ditert.-butyl-para-cresol til det vandige medium før dispergeringen av monomeren eller monomerene er vanligvis fra ca. 0,005 til 0,05 vekt-£, beregnet på vekten av monomeren. The addition of 2,6-di-tert-butyl-para-cresol to the aqueous medium prior to the dispersion of the monomer or monomers is usually from ca. 0.005 to 0.05 wt-£, calculated on the weight of the monomer.
2,6-ditert.-butyl-para-cresol, tilsatt til reaksjonsmediet under polymeriseringen, utgjør vanligvis fra ca. 0,005 til 0,05 vekt-5É, beregnet på vekten av monomer eller monomerer, og benyttes fortrinnsvis i form av en vandig dispersjon eller 1 oppløsning i en lavmolekylvekts alifatisk alkohol slik som 2,6-di-tert.-butyl-para-cresol, added to the reaction medium during the polymerization, usually amounts from approx. 0.005 to 0.05 weight-5É, calculated on the weight of monomer or monomers, and is preferably used in the form of an aqueous dispersion or 1 solution in a low molecular weight aliphatic alcohol such as
for eksempel metylalkohol eller etylalkohol. Innholdet av 2,6-ditert.-butyl-para-cresol I den vandige dispersjon er generelt fra ca. 0,01 til 1 vekt-#. Innholdet i den vandige oppløsning er generelt fra ca. 5 til 15 vekt-%. for example methyl alcohol or ethyl alcohol. The content of 2,6-di-tert.-butyl-para-cresol in the aqueous dispersion is generally from approx. 0.01 to 1 weight #. The content of the aqueous solution is generally from approx. 5 to 15% by weight.
Som benyttet heri betyr vlnylklorid- "polymerer" homo- og kopolymerer av vlnylklorid idet de siste inneholder minst 50 vekt-# vlnylklorid og minst en monomer som er kopolymeriser-bar dermed. Den kopolymeriserbare monomer er en som generelt benyttes i standardteknikker for kopolymerisering av vlnylklorid. Eksempler er vinylestere av mono- og polykarboksylsyrer som vinylacetat, propionat, benzoat; umettede mono- og polykarboksylsyrer slik som akryl-, metakryl-, malein-, fumar- og itakonsyrer, såvel som disses alifatiske, cykloalifatiske og aromatiske estre, deres amider, deres nitriler; allyl-, vinyl- og vinyliden halogenider; alkyl-vinyletere; og olefinene. As used herein, vinyl chloride "polymers" mean homo- and copolymers of vinyl chloride, the latter containing at least 50 wt% vinyl chloride and at least one monomer that is copolymerizable with it. The copolymerizable monomer is one generally used in standard techniques for copolymerizing vinyl chloride. Examples are vinyl esters of mono- and polycarboxylic acids such as vinyl acetate, propionate, benzoate; unsaturated mono- and polycarboxylic acids such as acrylic, methacrylic, maleic, fumaric and itaconic acids, as well as their aliphatic, cycloaliphatic and aromatic esters, their amides, their nitriles; allyl, vinyl and vinylidene halides; alkyl vinyl ethers; and the olefins.
I henhold til oppfinnelsens fremgangsmåte kan man benytte alle de organoppløselige polymerlserlngslnltlatorer som kan benyttes for fremstilling 1 mikrosuspensjon av vlnylklorid polymerer, og representeres ved dannelsen av frie radikaler slik som organiske peroksyder slik som laurylperoksyd, acetylcykloheksansulfonylperoksyd, isobutyroylperoksyd, dikloracetylperoksyd, trikloracetylperoksyd, peroksydikarbon-ater som etylperoksydikarbonat, etylheksylperoksydiakarbonat, isopropyl peroksydikarbonat, isobutylperoksydikarbonat; tert.-butylpermetoksyacetat; tert.-butylperetoksyacetat; tert.-butylperfenoksy-2-propionat. Hver polymeriseringsinitiator, danner av frie radikaler, kan uttrykkes som aktivt oksygen. Når det gjelder en peroksydforbindelse frigir et molekyl av peroksydforbindelsen et oksygenion ved dekomponer-ing, det vil si tilsvarende et atom aktivt oksygen. Når det gjelder polymeriseringsinitiatoren, en friradikal-danner forskjellig fra en peroksydforbindelse, er det akseptert å uttrykke denne som aktivt oksygen ved å ta i betraktning på samme måte at et molekyl av polymeriseringsinitiatoren tilsvarer et atom aktivt oksygen. According to the method of the invention, one can use all the organosoluble polymer solvents that can be used for the production of a microsuspension of vinyl chloride polymers, and is represented by the formation of free radicals such as organic peroxides such as lauryl peroxide, acetylcyclohexanesulfonyl peroxide, isobutyroyl peroxide, dichloroacetyl peroxide, trichloroacetyl peroxide, peroxydicarbonates which ethyl peroxydicarbonate, ethylhexyl peroxydicarbonate, isopropyl peroxydicarbonate, isobutyl peroxydicarbonate; tert-butyl permethoxyacetate; tert-butyl perethoxyacetate; tert-butylperphenoxy-2-propionate. Each polymerization initiator, formed by free radicals, can be expressed as active oxygen. In the case of a peroxide compound, a molecule of the peroxide compound releases an oxygen ion upon decomposition, i.e. equivalent to an atom of active oxygen. As for the polymerization initiator, a free radical generator other than a peroxide compound, it is accepted to express this as active oxygen by taking into account in the same way that one molecule of the polymerization initiator corresponds to one atom of active oxygen.
Valget av organooppløselig initiator avhenger av dekomponer-ingshastigheten ved den valgte reaksjonstemperatur. Initiatoren må således være tilstrekkelig reaktiv til at den ved bruk av 0,004 - 0,16 vekt-%, beregnet på monomer eller monomerer, av inltiatoren, uttrykt som aktivt oksygen, kan gjennomføre fremstilling av lateksen i løpet av mellom 4 og 20 timer. Imidlertid må reaksjonshastigheten ikke være for høy slik at mengden initiator som dekomponeres under fremstilling av lateksen, ikke overskrider halvparten av den benyttede initiatormengde. For å oppnå dette er det således nødvendig å velge en initiator hvis halveringstid er slik at forholdet mellom initiator som destrueres under fremstilling av lateksen ligger mellom 1 og 50 vekt-# av den totalt benyttede mengde initiator. Når man benytter flere organo-oppløselige Initiatorer er det av fordel å velge dem med forskjellig reaktivitet: den mest reaktive initiator virker prinsippielt under fremstilling av lateksen ifølge oppfinnelsen mens den minst reaktive initiator prinsippielt reagerer under polymeriseringen i podet mikrosuspensjon, oppnådd ut fra fremstillingen av vinylklorid-polymerene 1 nærvær av lateksen som benyttes som podingsprodukt. The choice of organosoluble initiator depends on the decomposition rate at the selected reaction temperature. The initiator must thus be sufficiently reactive so that when using 0.004 - 0.16% by weight, calculated on monomer or monomers, of the initiator, expressed as active oxygen, it can carry out production of the latex within between 4 and 20 hours. However, the reaction rate must not be too high so that the amount of initiator that is decomposed during the production of the latex does not exceed half of the amount of initiator used. In order to achieve this, it is thus necessary to choose an initiator whose half-life is such that the ratio of initiator that is destroyed during the production of the latex is between 1 and 50 by weight of the total amount of initiator used. When using several organo-soluble initiators, it is advantageous to choose them with different reactivity: the most reactive initiator works in principle during the production of the latex according to the invention, while the least reactive initiator in principle reacts during the polymerization in the grafted microsuspension, obtained from the production of vinyl chloride -the polymers 1 presence of the latex used as grafting product.
Den mest egnede initiator eller initiatorer som kan benyttes for hver spesiell homo- eller kopolymerisering og mengden derav, kan bestemmes ved rutineforsøk. The most suitable initiator or initiators that can be used for each particular homo- or copolymerization and the amount thereof can be determined by routine experiments.
Mengden vann som benyttes ifølge oppfinnelsen er slik at de opprinnelige innhold monomer eller monomerer i reaksjonsmediet generelt ligger mellom ca. 30 og 50 vekt-&. The amount of water used according to the invention is such that the original content of monomer or monomers in the reaction medium is generally between approx. 30 and 50 weight-&.
Det anioniske emulgeringsmidlet som benyttes er spesielt representert ved såper av fettsyrer, alkylsulfater, alkylsul-fonater, alkylarylsulfonater, alkylsulfosuccinater, de alkalisk alkylfosfater og ikke-ionisk emulgeringsmidler av polykondensater av etylen- eller polypropylenoksyd med forskjellige hydroksylerte organiske forbindelser. Det kan være fordelaktig på samme måte å tilsette emulgeringsmidlet eller midlene til reaksjonsmediet i løpet av polymeriseringen. Mengden emulgeringsmlddel ligger generelt mellom ca. 0,3 og 4 vekt-#, beregnet på mengden monomer eller monomerer. Dispersjonen av monomer eller monomerer i det vandige medium dannes ved en temperatur generelt mellom 10 og 30°C ved hjelp av mekaniske midler som en kolloidmølle, en høyhastighetspumpe, vibreringsanordninger, ultralydapparater og lignende. The anionic emulsifier used is particularly represented by soaps of fatty acids, alkyl sulphates, alkyl sulphonates, alkyl aryl sulphonates, alkyl sulphosuccinates, the alkaline alkyl phosphates and non-ionic emulsifiers of polycondensates of ethylene or polypropylene oxide with various hydroxylated organic compounds. It may be advantageous in the same way to add the emulsifier or agents to the reaction medium during the polymerization. The amount of emulsifying agent is generally between approx. 0.3 and 4 by weight #, calculated on the amount of monomer or monomers. The dispersion of monomer or monomers in the aqueous medium is formed at a temperature generally between 10 and 30°C by means of mechanical means such as a colloid mill, a high-speed pump, vibrating devices, ultrasonic devices and the like.
Polymeriseringstrinnet gjennomføres under autogent trykk og moderat omrøring ved å øke temperaturen i dispersjonen som oppnås til den tilsiktede polymeriseringstemperatur 0^, generelt mellom ca. 30 og 65°C, deretter ved tilsetning av 2,6-ditert.-butyl-para-cresol kontinuerlig til reaksjonsmediet når temperaturen 63 i mediet er slik at temperaturforskjellen er over en verdi valgt innen området 0 - +5"C og fortrinnsvis 0 - + 2' C. Etter det vanlige trykkfallet blir reaksjonen stanset og ikke-omdannet monomer eller monomerer fjernes ved avgassing. The polymerization step is carried out under autogenous pressure and moderate stirring by increasing the temperature of the dispersion which is achieved to the intended polymerization temperature 0°, generally between approx. 30 and 65°C, then by adding 2,6-di-tert.-butyl-para-cresol continuously to the reaction medium when the temperature 63 in the medium is such that the temperature difference is above a value chosen within the range 0 - +5"C and preferably 0 - + 2' C. After the usual pressure drop, the reaction is stopped and unconverted monomer or monomers are removed by degassing.
Oppfinnelsen skal forklares videre i forbindelse med de følgende eksempler der eksemplene 1, 3, 4, 5 og 6 er sammenllgningseksempler og eksempel 2 er ifølge oppfinnelsen. The invention shall be further explained in connection with the following examples where examples 1, 3, 4, 5 and 6 are comparative examples and example 2 is according to the invention.
Eksempel 1; Sammenligning Example 1; Comparison
Følgende bestanddeler blandes: The following ingredients are mixed:
i) 40 kg vlnylklorid i) 40 kg of woolnyl chloride
il) 0,6 kg lauroylperoksyd; 11) 0.6 kg of lauroyl peroxide;
ili) 4 kg av en vandig oppløsning av 10 vekt-56 natrium ili) 4 kg of an aqueous solution of 10 wt-56 sodium
dodecylbenzensulfonat; og dodecylbenzene sulfonate; and
iv) vann i en slik mengde av vinylklorid-innholdet i iv) water in such quantity of the vinyl chloride content i
blandingen er 43 vekt-£. the mixture is 43 wt.-lb.
En fin dispersjon av vlnylklorid dannes i det vandige medium og deretter innføres dispersjonen i en dobbeltkappet autoklav med kapasitet 120 1, utstyrt med et røreverk med anker. Reaksjonsmediet som således dannes bringes til den ønskede polymeriseringstemperatur G^ på 52°C under autogent trykk idet omrøringshastigheten er 50 omdr./minutt. A fine dispersion of woolnyl chloride is formed in the aqueous medium and then the dispersion is introduced into a double-jacketed autoclave with a capacity of 120 1, equipped with an anchor stirrer. The reaction medium which is thus formed is brought to the desired polymerization temperature G^ of 52°C under autogenous pressure, the stirring speed being 50 rpm.
Etter trykkfallet, det vil sl etter 9 timer, blir lkke-omsatt vlnylklorid avgasset. En lateks oppnås og tørrstoffinnholdet utgjør 40 vekt-# og partiklene har en midlere diameter på 0,4 pm og inneholder 1,4 vekt-56, beregnet på polymeren, av lauroylperoksyd. After the pressure drop, which will be after 9 hours, unreacted vinyl chloride is degassed. A latex is obtained and the solids content is 40 wt-# and the particles have an average diameter of 0.4 µm and contain 1.4 wt-56, calculated on the polymer, of lauroyl peroxide.
Eksempel 2 Example 2
Prosedyren i Eks. 1 ble gjennomført men før dannelse av den fine disersjon av vlnylklorid i det vandige medium ble det tilsatt 2 ,6-ditert.-butyl-para-cresol, DBPC, til mediet, og under polymeriseringen ble det tilsatt ytterligere DBPC, kontinuerlig, når temperaturen ©2 i reaksjonsmediet var over 53"C. Det DBPC som ble tilsatt under polymeriseringen ble benyttet i form av en dispersjon 12 1 vann. The procedure in Ex. 1 was carried out but before formation of the fine dispersion of vinyl chloride in the aqueous medium, 2,6-di-tert-butyl-para-cresol, DBPC, was added to the medium, and during the polymerization further DBPC was added, continuously, when the temperature ©2 in the reaction medium was above 53°C. The DBPC that was added during the polymerization was used in the form of a dispersion of 12 1 water.
Eksemplene 3 og 4: Sammenligning Examples 3 and 4: Comparison
Prosedyren i Eks. 2 ble gjennomført bortsett fra at DBPC ble erstattet med hydrokinon, HQ. The procedure in Ex. 2 was carried out except that DBPC was replaced with hydroquinone, HQ.
Eksemplene 5 og 6: Sammenlignig Examples 5 and 6: Comparative
Prosedyren i Eks. 2 ble gjennomført bortsett fra at DBPC ble erstattet med metylhydroquinon, MEHQ. The procedure in Ex. 2 was carried out except that DBPC was replaced with methylhydroquinone, MEHQ.
Tabell I nedenfor angir for hvert eksempel: Table I below indicates for each example:
i) arten av benyttet additiv (DBPC, HQ eller MEHQ), i) the nature of the additive used (DBPC, HQ or MEHQ),
ii) mengden benyttet additiv før realisering av dispersjonen; ii) the amount of additive used prior to the realization of the dispersion;
ili) additiv benyttet under polymeriseringen; ili) additive used during the polymerization;
iv) mengden skorpe som ble dannet under dispersjons-dannelsen; iv) the amount of crust formed during dispersion formation;
v) mengden skorpe dannet under polymeriseringen; og v) the amount of crust formed during the polymerization; and
vi) maksimal temperaturforskjell 02-©!, oppnådd under polymeriseringen. vi) maximum temperature difference 02-©!, obtained during the polymerization.
Claims (9)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8604763A FR2596763B1 (en) | 1986-04-03 | 1986-04-03 | PROCESS FOR THE PREPARATION OF HOMO- AND COPOLYMERS OF VINYL CHLORIDE IN MICROSUSPENSION FOR USE AS SEEDING PRODUCTS |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| NO870966D0 NO870966D0 (en) | 1987-03-09 |
| NO870966L NO870966L (en) | 1987-10-05 |
| NO168249B true NO168249B (en) | 1991-10-21 |
| NO168249C NO168249C (en) | 1992-01-29 |
Family
ID=9333844
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO870641A NO870641D0 (en) | 1986-04-03 | 1987-02-18 | Catalyst system containing a peroxide and an amine. |
| NO870966A NO168249C (en) | 1986-04-03 | 1987-03-09 | PREPARATION OF LATEXES OF VINYL CHLORIDE POLYMERS. |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO870641A NO870641D0 (en) | 1986-04-03 | 1987-02-18 | Catalyst system containing a peroxide and an amine. |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US4868258A (en) |
| EP (1) | EP0240415B1 (en) |
| JP (2) | JPH07107081B2 (en) |
| KR (1) | KR930004607B1 (en) |
| CN (1) | CN1008370B (en) |
| DE (1) | DE3766278D1 (en) |
| ES (1) | ES2018837B3 (en) |
| FI (1) | FI89269C (en) |
| FR (1) | FR2596763B1 (en) |
| IN (1) | IN169521B (en) |
| NO (2) | NO870641D0 (en) |
| PT (1) | PT84614B (en) |
| ZA (1) | ZA872369B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4654392A (en) * | 1985-07-12 | 1987-03-31 | The Goodyear Tire & Rubber Company | BHA in vinyl chloride polymerization |
| EP0810240A1 (en) * | 1996-05-31 | 1997-12-03 | Elf Atochem S.A. | Latex of vinyl chloride copolymers with a special structure, its preparation process and uses |
| US6599966B2 (en) | 2000-12-15 | 2003-07-29 | General Electric Company | Polycarbonate-polyester compositions with enhanced flow |
| KR101445240B1 (en) * | 2012-11-02 | 2014-09-29 | 한화케미칼 주식회사 | Polyvinyl chloride based resin and Method for preparing the same |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2662867A (en) * | 1951-03-29 | 1953-12-15 | Goodrich Co B F | Method of stabilizing aqueous dispersions of haloethylene polymers |
| FR1485547A (en) * | 1966-01-19 | 1967-06-23 | Pechiney Saint Gobain | Continuous process of polymerization of vinyl chloride |
| US3642756A (en) * | 1969-08-22 | 1972-02-15 | Dow Chemical Co | Method for increasing the capacity of a polymerization vessel during polymerization of vinyl chloride monomer in aqueous suspension |
| JPS4921304A (en) * | 1972-06-21 | 1974-02-25 | ||
| JPS5129530B2 (en) * | 1972-06-28 | 1976-08-26 | ||
| US4180634A (en) * | 1975-07-18 | 1979-12-25 | Shin-Etsu Chemical Co., Ltd. | Polymerizing vinyl chloride with lowering of scale formation |
| US4482684A (en) * | 1981-04-30 | 1984-11-13 | The B. F. Goodrich Company | Process for polymerization of vinyl monomers with improved kinetic rate profile |
| US4478986A (en) * | 1981-07-06 | 1984-10-23 | Ciba-Geigy Corporation | Tri-N-substituted-s-triazine-trione chain terminator for polyvinyl chloride polymerization |
| US4401798A (en) * | 1982-04-22 | 1983-08-30 | Tenneco Polymers, Inc. | Process for the production of vinyl halide polymers that uses an alkyl-substituted trisphenol as the chain-terminating agent |
| US4654392A (en) * | 1985-07-12 | 1987-03-31 | The Goodyear Tire & Rubber Company | BHA in vinyl chloride polymerization |
-
1986
- 1986-04-03 FR FR8604763A patent/FR2596763B1/en not_active Expired
-
1987
- 1987-02-18 NO NO870641A patent/NO870641D0/en unknown
- 1987-03-09 NO NO870966A patent/NO168249C/en not_active IP Right Cessation
- 1987-03-24 US US07/029,741 patent/US4868258A/en not_active Expired - Lifetime
- 1987-03-25 DE DE8787400665T patent/DE3766278D1/en not_active Expired - Fee Related
- 1987-03-25 EP EP87400665A patent/EP0240415B1/en not_active Expired - Lifetime
- 1987-03-25 ES ES87400665T patent/ES2018837B3/en not_active Expired - Lifetime
- 1987-04-01 ZA ZA872369A patent/ZA872369B/en unknown
- 1987-04-02 JP JP62079838A patent/JPH07107081B2/en not_active Expired - Lifetime
- 1987-04-02 PT PT84614A patent/PT84614B/en not_active IP Right Cessation
- 1987-04-02 FI FI871455A patent/FI89269C/en not_active IP Right Cessation
- 1987-04-02 IN IN240/MAS/87A patent/IN169521B/en unknown
- 1987-04-03 CN CN87102591A patent/CN1008370B/en not_active Expired
- 1987-04-03 KR KR1019870003190A patent/KR930004607B1/en not_active IP Right Cessation
-
1994
- 1994-09-16 JP JP6222092A patent/JP2781728B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| NO870966L (en) | 1987-10-05 |
| FI89269C (en) | 1993-09-10 |
| JPH07165805A (en) | 1995-06-27 |
| FR2596763A1 (en) | 1987-10-09 |
| US4868258A (en) | 1989-09-19 |
| JPH07107081B2 (en) | 1995-11-15 |
| ES2018837B3 (en) | 1991-05-16 |
| NO870641D0 (en) | 1987-02-18 |
| JPS62250011A (en) | 1987-10-30 |
| EP0240415B1 (en) | 1990-11-22 |
| KR870010095A (en) | 1987-11-30 |
| CN87102591A (en) | 1987-10-14 |
| ZA872369B (en) | 1987-12-30 |
| DE3766278D1 (en) | 1991-01-03 |
| PT84614B (en) | 1989-11-30 |
| FI871455A (en) | 1987-10-04 |
| JP2781728B2 (en) | 1998-07-30 |
| NO168249C (en) | 1992-01-29 |
| EP0240415A1 (en) | 1987-10-07 |
| FI89269B (en) | 1993-05-31 |
| FR2596763B1 (en) | 1988-06-03 |
| FI871455A0 (en) | 1987-04-02 |
| CN1008370B (en) | 1990-06-13 |
| NO870966D0 (en) | 1987-03-09 |
| PT84614A (en) | 1987-05-01 |
| IN169521B (en) | 1991-11-02 |
| KR930004607B1 (en) | 1993-06-01 |
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